Enantioselective Chromatographic Methods for Detection of Fungicides in Complex Environmental Matrices: Advances and Applications

Many organic fungicides are chiral and are used in diverse application areas, including pharmaceuticals, personal care products, agrochemicals, and industry. Fungicides have valuable effects such as preventing fungal infestations and the treatment of diseases, but their generalized use resulted in their occurrence in diverse environmental compartments which is an increasing environmental concern with negative impact on non-target organisms and human health risks. Besides, enantiomers of chiral fungicides may exhibit distinct bioactivity including toxicity and degradation profiles. Therefore, monitoring their enantioselective occurrence in the environment is essential to accurately assess enantioselective (eco)toxicity and establish environmental quality standard levels. This review provides the first comprehensive and critically interpretative assessment of enantioselective chromatographic methods for the determination of fungicides, with a primary focus on azole compounds, in complex environmental matrices (e.g., soil, sediment, plants, earthworms, sewage sludge, water, wastewater) due to their regulatory relevance in the EU Watch Lists, frequent occurrence in environmental matrices, and specific analytical challenges associated with their chiral nature. Other fungicide classes are also included, since other fungicides (either chiral or achiral) reported in the articles retrieved by the literature search, were also evaluated, integrating methodological, analytical and regulatory dimensions. Liquid chromatography was identified as the predominant analytical technique, with polysaccharide-based chiral stationary phases being the most frequently used, while sample preparation was mainly based on solid-phase extraction and QuEChERS-based approaches for complex environmental matrices. Analytical performance parameters were compared to highlight strengths and limitations of reported methods, while environmental monitoring data were reviewed, identifying soil and water as matrices with the highest reported chiral fungicide levels. The urgent need to develop robust enantioselective analytical methods to recognize the distinctive biological and toxicological properties of individual enantiomers are critically discussed. By revealing persistent gaps in enantioselective workflows and regulatory differentiation between enantiomers, it highlights the need for robust analytical approaches and reliable monitoring strategies to contribute for future enantiomer-specific environmental risk assessment frameworks.